CN102382304A - Method for preparing poly(phenylene cyanide sulfide) resin - Google Patents
Method for preparing poly(phenylene cyanide sulfide) resin Download PDFInfo
- Publication number
- CN102382304A CN102382304A CN2011102633113A CN201110263311A CN102382304A CN 102382304 A CN102382304 A CN 102382304A CN 2011102633113 A CN2011102633113 A CN 2011102633113A CN 201110263311 A CN201110263311 A CN 201110263311A CN 102382304 A CN102382304 A CN 102382304A
- Authority
- CN
- China
- Prior art keywords
- sulfide resin
- preparation
- reaction
- polyphenyl
- polyphenyl nitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 *C1C=CC=*(*)C1C#N Chemical compound *C1C=CC=*(*)C1C#N 0.000 description 2
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a method for preparing poly(phenylene cyanide sulfide) resin. The method comprises the following steps of: pouring an alkali metal sulfide to a polar organic solvent; stirring in the atmosphere of an inert gas and adding phenyldihalide carbonitrile and lithium chloride; raising the temperature of a reaction system to the boiling point of the polar organic solvent; continuously stirring for 2 hours to 10 hours at the temperature of the boiling point; filtering the obtained products; alternately washing a solid obtained by filtering with boiling water and the organic solvent; and drying the solid. In the method for preparing the poly(phenylene cyanide sulfide) resin, raw materials are easy to obtain, the reaction conditions are easy to realize, the production process is easy to control, the reaction activity is high, and the high molecular weight poly(phenylene cyanide sulfide) resin can be stably obtained at atmospheric pressure and is suitable for large-scale industrial production. A product obtained by the method is especially suitable for various fields of aerospace, electronics, machinery, chemical engineering, and the like.
Description
Technical field
The present invention relates to poly (arylene ether nitrile) resin, particularly a kind of preparation method of polyphenyl nitrile sulfide resin.
Background technology
Special engineering plastics is owing to its excellent physics, chemical property are widely used in fields such as aerospace, electronic apparatus, machinofacture in recent years, and one of this wherein most typical representative kind is exactly a polyphenylene sulfide.Polyphenylene sulfide is a kind of crystalline polymkeric substance; Have good high temperature resistant, corrosion-resistant, radiation hardness, fire-retardant, isostatic physical and mechanical properties and fabulous dimensional stability and good characteristics such as electrical property; Be widely used as structural macromolecular material, through being widely used as special engineering plastics after filling, the modification.Simultaneously, also can be made into various functional films, coating and matrix material, succeed in fields such as electronic apparatus, aerospace, automobile transportations and use.
Although polyphenylene sulfide has numerous advantages; But exist the some shortcomings part; This mainly shows following two aspects: the one, and temperature resistant grade is on the low side, and its second-order transition temperature is merely 92 ℃, and the product life-time service temperature after enhancing modified also generally is lower than 200 ℃; The 2nd, fragility is bigger, and unit elongation is low, and this has just limited its use as shock-resistant parts.In order to overcome above deficiency; Various countries' researcher poly-p-phenylene sulfide ether resin has carried out the research of various synthesis modifications, has developed like U.S. Phillips Petroleum company that PPSS, Japanese Wu Yu chemical industrial company have been developed polyphenylene sulfide ketone, Japanese Tosoh company has developed polyphenylene sulfide acid amides etc.These kinds all are to introduce the polymkeric substance of processing behind the strong polar group on the main chain of polyphenylene sulfide, belonging to polyphenylene sulfide backbone structure modification kind.
Polyphenyl nitrile thioether belongs to polyphenylene sulfide side group modification kind; It is on the phenyl ring of polyphenylene sulfide, to introduce the polarity side group; The remarkable improvement of the resistance toheat of polyphenylene sulfide; Keep excellent mechanical property simultaneously, the Application Areas of product is able to be extended to numerous areas such as aerospace, electronic apparatus, machinery, chemical industry.
Now, the various functionalization investigations of materials of p-poly-phenyl thioether are comparatively rapid in the world, and part developed country polyphenylene sulfide and modifier thereof are in automobile, field widespread use such as electric.But in China, only there is a spot of inorganic filling enhancing modified polyphenylene sulfide kind to sell at present, the main dependence on import of the market requirement, domestic enterprise can't be born for the high price of product import and other severe condition.
The Progress in synthesis of polyphenylene sulfide is slow on the one hand, and the preparation method of polyphenyl nitrile thioether is monopolized by Japan and other countries on the other hand.
It is the problem that the present invention tries hard to solve that a kind of preparation method with polyphenyl nitrile thioether of better industrial prospect is provided.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyphenyl nitrile thioether; Its raw material is easy to get; Condition is prone to control, and reactive behavior is high, under normal pressure, gets final product stable acquisition high-molecular weight polyphenyl nitrile sulfide resin product; And products obtained therefrom resistance toheat and mechanical property are excellent, and the industrial applications of method has a extensive future.
The objective of the invention is to realize through following scheme:
A kind of preparation method of polyphenyl nitrile sulfide resin; Said polyphenyl nitrile sulfide resin has the repeating unit shown in
, and said method comprises the steps:
(1) it is subsequent use to get raw material, reaction solvent and dewatering agent, and raw material comprises phenyl-dihalide formonitrile HCN and alkali metalsulphide, and reaction solvent is a polar organic solvent, and said dewatering agent comprises toluene or YLENE;
(2) alkali metalsulphide is dropped in the said reaction solvent, stir down and adding phenyl-dihalide formonitrile HCN in inert gas atmosphere again, get reaction system;
(3) in step (2) gained reaction system, add lithium chloride, the boiling point of the temperature of the reaction system that raises then to reaction solvent, and under this boiling temperature, continue to stir 2-10 hour, get reactant;
Because of polyphenyl nitrile sulfide resin belongs to semicrystalline polymer, in reaction process, be prone to and separate out phenomenon, be unfavorable for the stable raising of molecular resin amount; In the prior art; The reaction of phenyl-dihalide formonitrile HCN and alkali metalsulphide is under pressurized conditions, to carry out; The purpose of pressurization is exactly in order to improve solvent to dissolving resin property; And then the stable raising of assurance molecular resin amount, but compressive reaction is very high to the conversion unit requirement, and reaction process is prone to fluctuation; The present invention adopts and adds lithium chloride auxiliary agent raising reaction solvent to dissolving resin property, has avoided compressive reaction, has improved the stability of reaction process, and reaction is easier to control;
(4) filter said reactant, and after replacing the solid of washing and filtering gained with boiling water and organic solvent, drying obtains required polyphenyl nitrile sulfide resin.
In the step (4), the purpose of washing is to remove the solvent that impurity and product surface adhere to, and said impurity comprises byproduct of reaction alkali metal halide, residual raw material and micromolecular compound.The reaction base metal halide that boiling water adheres on can the flush away product; Because alkali metal halide and resin physics mix; Boiling water helps improving solvability; Thereby improve detersive efficiency and effect, organic solvent mainly is the reaction raw materials and the oligopolymer of washing small amount of residual, and the two alternately washs can guarantee washing effect.The slip of single wash (be every employing boiling water or organic solvent washing once) back gained generally adopts spinning to handle; Spinning gained solid washs next time again; Wash and present the water white transparency state to organic solvent and washing water and get final product, the total degree of boiling water and organic solvent washing is 2-8 time generally speaking.
Reaction equation:
In this formula, x is Cl or F, and Y is Na, K or Li.
Prepared its second-order transition temperature of polyphenyl nitrile sulfide resin of the present invention is 169 ℃ of effects, and fusing point can reach 400 ℃, and temperature of initial decomposition is more than 540 ℃; Product has higher mechanical strength, and its tensile strength is at 110～140MPa, and flexural strength is at 120～150MPa, and modulus in flexure is at 3.6～3.8GPa, and notched Izod impact strength is at 9.5～14KJ/m
2, indexs such as its resistance toheat and mechanical property have been much better than traditional polyphenylene sulfide, have application prospects more.
Preferably, in the step (2), before the phenyl-dihalide formonitrile HCN adds; The alkali metalsulphide contained humidity is carried out processed, and said processed is after dropping into alkali metalsulphide in the said reaction solvent, adds dewatering agent toluene or YLENE; The dewatering agent consumption is generally about 10% of reaction solvent quality; Under inert gas atmosphere, stir again and carry out component distillation, treat that the alkali metalsulphide contained humidity is removed after, steam dewatering agent.Can add the phenyl-dihalide formonitrile HCN after steaming dewatering agent.Because of the alkali metalsulphide moisture absorption is strong, commercial product generally contains small amount of moisture, has therefore increased dehydration process steps in the present invention, to avoid being more conducive to industrializing implementation to bringing impurity in the reaction system into.
Azeotropic according to the invention is meant the azeotropic of reaction solvent and dewatering agent; The vapor zone of dewatering agent goes out moisture during azeotropic; Again through backflow make dewatering agent with moisture settlement separate come out in water trap; And remaining solvent continues to get back in the reactor drum, reaches the purpose that removes the metallic sulfide contained humidity.
Preferably, described phenyl-dihalide formonitrile HCN comprises 2,6-dichlorobenzonitrile and/or 2,6-difluorobenzonitrile; For the ease of the separation and the purification process of product, said phenyl-dihalide formonitrile HCN is generally got wherein a kind of.
Preferably, said reaction solvent comprises N-Methyl pyrrolidone, N, dinethylformamide and/or DMAC N,N; For the ease of the recycling of solvent, said reaction solvent is generally selected wherein a kind of for use.
Preferably, said alkali metalsulphide comprises sodium sulphite, lithium sulfide and/or potassium sulphide; For the ease of the separation and the purification process of product, alkali metalsulphide is generally got wherein a kind of.
Preferably, the said organic solvent of step (4) comprises acetone, methyl alcohol and/or ethanol; For the ease of the recycling of solvent, said organic solvent is generally selected wherein a kind of for use.
Preferably, the consumption of the said lithium chloride of step (3) is the 2-4% of reaction solvent quality.
Preferably, in the raw material, the phenyl-dihalide formonitrile HCN equates with the mol ratio of alkali metalsulphide.
The ratio of preferably, getting 1 liter of reaction solvent in every 100-400 gram raw material during reaction is fed in raw material.For large-scale production, the reaction solvent consumption is bigger to the reaction process influence, and the reaction solvent amount is prone to cause reactive behavior to reduce when too much, and the molecular resin amount is difficult to improve; Be prone to cause solvability to reduce when quantity of solvent is very few, resin is easy to separate out in reaction process, also is unfavorable for that the molecular resin amount improves simultaneously; For scheme of the present invention, it is comparatively suitable that the ratio of getting 1 liter of solvent in every 100-400 gram raw material is fed in raw material.
Preferably, in the step (4), the temperature of said organic solvent is not less than 55 degree, and the purpose of heating is in order to improve the solvability of organic solvent, better to improve washing effect.
Beneficial effect of the present invention:
The present invention has following advantage:
1, raw material of the present invention is easy to get, and reaction conditions is easy to realize that production process is easy to control.
2, adopt the phenyl-dihalide formonitrile HCN to substitute dichlorobenzene, increased substantially reactive behavior as body material, can stable acquisition high-molecular weight polyphenyl nitrile sulfide resin under normal pressure.
3, added lithium chloride in the reaction process, can effectively improve reaction solvent to dissolving resin property, avoided compressive reaction, made reaction conditions milder, reaction process is stability more, is easier to control.
4, the present invention imports strong polar itrile group as side group on polyphenylene sulfide main chain phenyl ring; Indexs such as its temperature resistant grade of polyphenyl nitrile sulfide resin that is obtained and mechanical property all are much better than traditional polyphenylene sulfide; It is a kind of novel special engineering plastics; Be specially adapted to numerous areas such as aerospace, electronic apparatus, machinery, chemical industry, application prospect is very extensive.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized.
Embodiment 1
In having the 100L reactor drum of water trap, whisking appliance and well heater, drop into 4.8Kg sodium sulphite (20mol), 4Kg toluene and 41LN-SL 1332, material temperature to 170 ℃ in stirring and the rising reactor drum under nitrogen protection, component distillation under this temperature; The sodium sulphite contained humidity is taken out of by toluene vapor during azeotropic; Again through backflow make toluene vapor with moisture settlement separate come out in water trap, and remaining solvent continues to get back in the reactor drum, treat that the alkali metalsulphide contained humidity is removed after; Under 170 ℃ of temperature, steam toluene; Then with load weighted 3.44Kg 2,6-dichlorobenzonitrile (20mol) and 1.2Kg lithium chloride drop in the reactor drum, keep in the reactor drum temperature of charge 203 ℃ of stirring reactions 6 hours; Stopped reaction gets reactant then.Filter said reactant, get solid product, alternately wash said solid product with boiling water and methyl alcohol again, said methanol temperature is 60 ℃.Slurry after the single wash all adopts the mode of spinning to handle; After washing 4 times altogether, drying gets purified polyphenyl nitrile sulfide resin 2.52Kg (yield 95%); Its performance is seen table 1, examination of infrared spectrum (KBr compressing tablet) test result: the c h bond 3030cm-1 and the 831cm-1 of phenyl ring; The C-C key 1590cm-1 of phenyl ring; Side group itrile group 2223cm-1 on the phenyl ring; Thioether bond 1095cm-1 and 735cm-1.
Table 1 polyphenyl nitrile sulfide resin performance
| Characteristic | Test condition, standard | Unit | The result |
| Limiting viscosity | 0.5g/dl, 140 ℃, the vitriol oil | dl/g | 0.61 |
| Second-order transition temperature | DSC，10℃/min | ℃ | 169 |
| Initial heat decomposition temperature | TGA, air | ℃ | 540 |
| Tensile strength | GB/T1040.2 | Mpa | 118 |
| Stretch percentage elongation | GB/T1040.2 | ％ | 21 |
| Flexural strength | GB/T9341 | Mpa | 135 |
| Modulus in flexure | GB/T9341 | GPa | 3.67 |
| Notched Izod impact strength | GB/T1043 | KJ/m2 | 10.5 |
Embodiment 2
In having the 100L reactor drum of water trap, whisking appliance and well heater, drop into 3.3Kg potassium sulphide (30mol), 7Kg toluene and 72L N-Methyl pyrrolidone, under nitrogen protection, stir and be warming up to 170 ℃, component distillation under this temperature; The potassium sulphide contained humidity is taken out of by toluene vapor; Again through backflow make toluene vapor with moisture settlement separate come out in water trap, remaining solvent continues to get back in the reactor drum, treat that the alkali metalsulphide contained humidity is removed after; Under 170 ℃ of temperature, steam toluene; With load weighted 4.17Kg 2,6-difluorobenzonitrile (30mol) and 1.44Kg lithium chloride drop in the reactor drum, keep in the reactor drum temperature of charge at 203 ℃ and stirring reaction after 2 hours; Stopped reaction obtains reactant.Filter said reactant, obtain solid product, the ethanol with boiling water and 60 ℃ alternately washs said solid product again; Slurry after the single wash all adopts the mode of spinning to handle; After washing 4 times altogether, drying gets purified polyphenyl nitrile sulfide resin 3.83Kg (yield 96%); Its performance is seen table 2, and examination of infrared spectrum (KBr compressing tablet) test result is consistent with embodiment 1.
Table 2 polyphenyl nitrile sulfide resin performance
| Characteristic | Test condition, standard | Unit | The result |
| Limiting viscosity | 0.5g/dl, 140 ℃, the vitriol oil | dl/g | 0.72 |
| Second-order transition temperature | DSC，10℃/min | ℃ | 170 |
| Initial heat decomposition temperature | TGA, air | ℃ | 540 |
| Tensile strength | GB/T1040.2 | Mpa | 128 |
| Stretch percentage elongation | GB/T1040.2 | ％ | 24 |
| Flexural strength | GB/T9341 | Mpa | 146 |
| Modulus in flexure | GB/T9341 | GPa | 3.69 |
| Notched Izod impact strength | GB/T1043 | KJ/m2 | 11 |
Embodiment 3
Embodiment 3
In having the 100L reactor drum of water trap, whisking appliance and well heater, drop into 4.8Kg sodium sulphite (20mol), 2Kg YLENE and 20L DMAC N,N, under nitrogen protection, stir and be warming up to 155 ℃; Component distillation under this temperature, the sodium sulphite contained humidity is taken out of by xylene steam during azeotropic, again through backflow make xylene steam with moisture settlement separate come out in water trap; Remaining solvent continues to get back in the reactor drum; After treating that the alkali metalsulphide contained humidity is removed, under 155 ℃ of temperature, steam YLENE, with load weighted 2.78Kg 2; 6-difluorobenzonitrile (20mol) and 0.8Kg lithium chloride drop in the reactor drum; After 10 hours, stopped reaction gets reactant to temperature of charge at 166 ℃ of stirring reactions in the maintenance reactor drum.The filtering reaction thing obtains solid product, alternately washs said solid product with boiling water and 55 ℃ of acetone again; Slurry after the single wash all adopts the mode of spinning to handle; After washing 4 times altogether, drying gets purified polyphenyl nitrile sulfide resin 2.94Kg (yield 96%); Its performance is seen table 3, and examination of infrared spectrum (KBr compressing tablet) test result is consistent with embodiment 1.
Table 3 polyphenyl nitrile sulfide resin performance
| Characteristic | Test condition, standard | Unit | The result |
| Limiting viscosity | 0.5g/dl, 140 ℃, the vitriol oil | dl/g | 0.53 |
| Second-order transition temperature | DSC，10℃/min | ℃ | 167 |
| Initial heat decomposition temperature | TGA, air | ℃ | 538 |
| Tensile strength | GB/T1040.2 | Mpa | 111 |
| Stretch percentage elongation | GB/T1040.2 | ％ | 19 |
| Flexural strength | GB/T9341 | Mpa | 132 |
| Modulus in flexure | GB/T9341 | GPa | 3.65 |
| Notched Izod impact strength | GB/T1043 | KJ/m2 | 9.8 |
Need explanation at last; Above embodiment only is used to explain technical scheme of the present invention and is unrestricted; Although technical scheme of the present invention is specified, it will be appreciated by those skilled in the art that and to make amendment or be equal to replacement technical scheme of the present invention with reference to preferred embodiment; And not breaking away from aim of the present invention and scope, it all should be encompassed in the middle of protection scope of the present invention.
Claims (10)
1. the preparation method of a polyphenyl nitrile sulfide resin; Said polyphenyl nitrile sulfide resin has the repeating unit shown in
, it is characterized in that: comprise the steps:
(1) it is subsequent use to get raw material, reaction solvent and dewatering agent, and raw material comprises phenyl-dihalide formonitrile HCN and alkali metalsulphide, and reaction solvent is a polar organic solvent;
(2) alkali metalsulphide is dropped in the said reaction solvent, stir down and adding phenyl-dihalide formonitrile HCN in inert gas atmosphere again, get reaction system;
(3) in step (2) gained reaction system, add lithium chloride, the boiling point of the temperature of the reaction system that raises then to reaction solvent, and under this boiling temperature, continue to stir 2-10 hour, get reactant;
(4) filter said reactant, replace the solid after drying of washing and filtering gained, obtain required polyphenyl nitrile sulfide resin with boiling water and organic solvent.
2. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: in the step (2), before the phenyl-dihalide formonitrile HCN adds; The alkali metalsulphide contained humidity is carried out processed; Said processed is after dropping into alkali metalsulphide in the said reaction solvent, adds dewatering agent toluene or YLENE, under inert gas atmosphere, stirs and carries out component distillation; After treating that the alkali metalsulphide contained humidity is removed, steam dewatering agent.
3. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: described phenyl-dihalide formonitrile HCN comprises 2,6-dichlorobenzonitrile and/or 2,6-difluorobenzonitrile.
4. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: said reaction solvent comprises N-Methyl pyrrolidone, N, dinethylformamide and/or DMAC N,N.
5. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: said alkali metalsulphide comprises sodium sulphite, lithium sulfide and/or potassium sulphide.
6. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: the said organic solvent of step (4) comprises acetone, methyl alcohol and/or ethanol.
7. the preparation method of polyphenyl nitrile sulfide resin according to claim 1 is characterized in that: the consumption of the said lithium chloride of step (3) is the 2-4% of reaction solvent quality.
8. according to the preparation method of the described polyphenyl nitrile of the arbitrary claim of claim 1 to 7 sulfide resin, it is characterized in that: in the raw material, the phenyl-dihalide formonitrile HCN equates with the mol ratio of alkali metalsulphide.
9. according to the preparation method of right 8 described polyphenyl nitrile sulfide resins, it is characterized in that: the ratio of getting 1 liter of reaction solvent in every 100-400 gram raw material during reaction is fed in raw material.
10. the preparation method of polyphenyl nitrile sulfide resin according to claim 9 is characterized in that: in the step (4), the temperature of organic solvent is not less than 55 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102633113A CN102382304A (en) | 2011-09-07 | 2011-09-07 | Method for preparing poly(phenylene cyanide sulfide) resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102633113A CN102382304A (en) | 2011-09-07 | 2011-09-07 | Method for preparing poly(phenylene cyanide sulfide) resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102382304A true CN102382304A (en) | 2012-03-21 |
Family
ID=45822178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102633113A Pending CN102382304A (en) | 2011-09-07 | 2011-09-07 | Method for preparing poly(phenylene cyanide sulfide) resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102382304A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766256A (en) * | 2012-07-31 | 2012-11-07 | 电子科技大学 | Bisphenol A type polyarylene sulfide ether nitrile resin and preparation method thereof |
| CN105601925A (en) * | 2016-01-19 | 2016-05-25 | 成都汇莹新材料有限公司 | Resin washing technique for production of polyphenylene sulfide |
| CN115975195A (en) * | 2023-03-03 | 2023-04-18 | 四川轻化工大学 | Polyphenylene sulfide nitrile and production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894434A (en) * | 1987-05-20 | 1990-01-16 | Tosoh Corporation | Polycyanoaryl thioether and preparation thereof |
| JPH0267321A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Polysulfide resin and preparation thereof |
| US4980454A (en) * | 1988-04-15 | 1990-12-25 | Tosoh Corporation | Poly(arylene cyano-thioether) copolymer and preparation thereof |
-
2011
- 2011-09-07 CN CN2011102633113A patent/CN102382304A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894434A (en) * | 1987-05-20 | 1990-01-16 | Tosoh Corporation | Polycyanoaryl thioether and preparation thereof |
| US4980454A (en) * | 1988-04-15 | 1990-12-25 | Tosoh Corporation | Poly(arylene cyano-thioether) copolymer and preparation thereof |
| JPH0267321A (en) * | 1988-08-31 | 1990-03-07 | Idemitsu Kosan Co Ltd | Polysulfide resin and preparation thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766256A (en) * | 2012-07-31 | 2012-11-07 | 电子科技大学 | Bisphenol A type polyarylene sulfide ether nitrile resin and preparation method thereof |
| CN105601925A (en) * | 2016-01-19 | 2016-05-25 | 成都汇莹新材料有限公司 | Resin washing technique for production of polyphenylene sulfide |
| CN105601925B (en) * | 2016-01-19 | 2018-01-16 | 成都汇莹新材料有限公司 | A kind of resin washing process technology in polyphenylene sulfide production |
| CN115975195A (en) * | 2023-03-03 | 2023-04-18 | 四川轻化工大学 | Polyphenylene sulfide nitrile and production method thereof |
| CN115975195B (en) * | 2023-03-03 | 2024-03-26 | 四川轻化工大学 | Polyphenylene sulfide nitrile and method for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311550A (en) | Esterifiable modification method of lignocelluloses and esterifiable modified lignocelluloses | |
| CN104231270A (en) | Method for preparing polyphenylene sulfide/graphene composite material through in situ polymerization | |
| CN102002138A (en) | Method for producing high-purity thermoplastic phenolic resin | |
| CN102766255A (en) | Polyaryl ether nitrile resin and industrialized synthetic method thereof | |
| JPWO2017051911A1 (en) | Process for producing purified lignin, purified lignin, resin composition and molded article | |
| CN102382304A (en) | Method for preparing poly(phenylene cyanide sulfide) resin | |
| CN113698593A (en) | Composite material and preparation method thereof | |
| CN106750302B (en) | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone | |
| CN107936250B (en) | Method for recycling polyphenylene sulfide oligomer | |
| CN113292703A (en) | Phosphorus-free full-bio-based flame-retardant epoxy resin with excellent thermal and mechanical properties and green preparation method thereof | |
| CN117362916A (en) | Modified phenolic resin and preparation method thereof | |
| CN102516527B (en) | Cyanopolyaryletherketone resin and its preparation method | |
| CN106380601A (en) | Purifying method for polyphenylene sulfide with high molecular weight | |
| CN102532532B (en) | Thioether-containing semi-aromatic polyamide and preparation method thereof | |
| CN111560106B (en) | Polyether-ether-ketone and preparation method thereof | |
| CN102898389A (en) | Method for recycling melamine waste residue | |
| CN101225168B (en) | Low melt-viscosity polyimide moulding powder and preparation method | |
| CN107286860A (en) | A kind of liquid crystal modified epoxy adhesive with conductive switch performance and preparation method thereof | |
| CN102417705A (en) | Modified polycarbonate composition for manufacturing capacitor shell | |
| CN102443165A (en) | Semiaromatic polyarylene sulfide amine and preparation method thereof | |
| CN102766256B (en) | Bisphenol A type polyarylene sulfide ether nitrile resin and preparation method thereof | |
| CN107915842B (en) | Preparation method of low-chlorine polyphenylene sulfide | |
| CN105175714A (en) | Process method for preparing cyano polyetherketoneketone resin | |
| CN116355211B (en) | Preparation method of phosphazene structure-containing phthalonitrile resin with self-catalytic characteristic | |
| CN116692852B (en) | Preparation method of coal-based diamond based on catalyst method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120321 |